2-(2-hydroxy-3-α-cumyl-5-nonylor 5-dodecylphenyl)-2H-benzotriazole

ABSTRACT

Soluble and thermally stable benzotriazole UV absorbers typified by those of formula I ##STR1## where R 1  is hydrogen or chloro, R 2  is alkyl or --CH 2  CH 2  COOR 4  where R 4  is hydrogen, alkyl or alkyl substituted with hydroxyl, and R 3  is α-cumyl, provide excellent light stability protection to electro coat, base coat or clear coat finishes. The new soluble, crystalline form of 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole is particularly effective.

This is a Divisional Ser. No. 08/424,843, filed Apr. 19, 1995.

The instant invention pertains to polymer film coating compositionsprotected against catastrophic failure by the presence of soluble andthermally stable benzotriazole UV absorbers; and to a new solublecrystalline form of2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole which isparticularly effective in such compositions.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 4,278,589 describes the preparation of2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole and2-(2-hydroxy-3-tert-octyl-5-α-cumylphenyl)-2H-benzotriazole. U.S. Pat.No. 4,278,589 also describes the preparation of2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole. This lattercompound is a very effective UV absorber, but unfortunately isrelatively insoluble being soluble only at about the 14% (by weight)level in xylene. Since such aromatic solvents are threatened withbanning because of environmental concerns, a diligent search for aneffective benzotriazole which has the general light stabilizingeffectiveness of 2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole andwhich is soluble in the new environmentally approved solvents isrequired. The several compounds mentioned earlier in this paragraph meetor essentially meet these new requirements.

Japanese Kokai 75/158588 describes the preparation of2-(2-hydroxy-3-α-cumyl-5-methylphenyl)-2H-benzotriazole and2-(2-hydroxy-3-methyl-5-α-cumylphenyl)-2H-benzotriazole as effective UVabsorbers.

U.S. Pat. No. 4,283,327 discloses the preparation of2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole and5-chloro-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole. U.S.Pat. Nos. 4,587,346; 4,675,352; 4,973,701; 5,095,062 and 5,240,975describe the preparation of liquid benzotriazole mixtures by the postalkylation of preformed benzotriazoles using higher alkenes and an acidcatalyst. Such products are complex liquid mixtures of various relatedbenzotriazoles and are soluble in the environmentally acceptablesolvents. However, while these UV absorbers are quite soluble inenvironmentally acceptable solvents, they do not have the thermalstability of the benzotriazole compounds which are substituted in the3-position by an α-cumyl moiety.

The instant benzotfiazole compounds are substituted in the 3-positionwith a α-cumyl group and in the 5-position usually with either a mixturewith various alkylated moieties as substituents or are single compoundssubstituted with one bulky, tert-alkyl group. These materials are moresoluble in common coatings solvents than the tris-aryl-s-triazines thatare functionalized with simple alkyl groups. Common coatings solventsinclude xylene, methyl amyl ketone, butyl cellosolve, butyl carbitol andmethyl isobutyl ketone. This functionality in combination with the highmolecular weight of the compounds provides the instant compounds with alow migratory propensity when incorporated into the base coat of a clearcoat/base coat system.

OBJECTS OF THE INVENTION

The object of this invention is to provide a method for protecting anelectro coat/base coat/clear coat coating system against delaminationfrom a substrate by incorporating therein a selected soluble andthermally stable benzotriazole.

Another object of this invention is to provide a new soluble crystallineform of 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.

Still another object of this invention is to provide organic orphotographic compositions stabilized against the deleterious effects ofactinic light using the new soluble benzotriazoles substituted in the3-position of the phenyl ring by an α-cumyl moiety.

DETAILED DISCLOSURE

The instant invention pertains to a new soluble crystalline form of2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, that is acompound of formula I ##STR2## wherein R₁ is hydrogen, R₂ is tert-octyland R₃ is α-cumyl.

This compound of formula I is useful as a stabilizer for organicpolymers as taught in U.S. Pat. No. 4,278,589. This compound of formulaI is disclosed in said patent in

Example 18 as being an off-white powder melting at 88°-90° C. As such,the powdery product has defects in terms of handling and apparentdensity, exhibiting poor flowability, meterability and storagestability.

It has now been found that the compound of formula I can be obtained ina different crystalline modification as purified crystalline particleswhich exhibit acceptable properties in respect to handling, apparentdensity, flowability, meterability and storage stability.

The new modification is characterized by a novel crystalline form asoff-white crystals melting in the range of 109°-111° C.; and by an X-raydiffraction pattern obtained using Cu-Kα which exhibits diffractionangles (2Θ) as seen below:

    ______________________________________                                        Peak No.     Diffraction Angle                                                ______________________________________                                        1            9.6                                                              2            10.2                                                             3            10.4                                                             4            10.8                                                             5            12.8                                                             6            13.8                                                             7            14.2                                                             8            14.8                                                             9            15.0                                                             10           16.4                                                             11           16.8                                                             12           17.8                                                             13           18.0                                                             14           18.6                                                             15           19.0                                                             16           19.4                                                             17           19.8                                                             18           20.2                                                             19           20.6                                                             20           21.2                                                             21           21.4                                                             22           23.0                                                             23           23.4                                                             24           24.6                                                             25           26.0                                                             26           28.0                                                             27           29.0                                                             28           30.4                                                             29           31.0                                                             ______________________________________                                    

The instant compound of formula I can also be obtained as in anamorphous modification having excellent solubility characteristics.

The instant invention also relates to a process for the preparation ofthis novel soluble crystalline modification of the compound of formula Iwhich comprises dissolving the compound in an aromatic solvent andprecipitating the compound by the addition of a lower alkanol; or byrecrystallizing the compound from a lower alkanol alone in conjunctionwith a minor (up to 10% by volume) of toluene.

The instant invention also pertains to a composition stabilized againstthermal, oxidative and actinic induced degradation which comprises

(a) an organic material subject to thermal, oxidative or actinic induceddegradation, and

(b) an effective stabilizing amount (generally about 0.01 to about 5% byweight of the stabilized composition) of the soluble crystalline form of2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,characterized by melting in the range of 109°-111° C. and by an X-raydiffraction pattern obtained using a Cu-Kα which exhibits diffractionangles (2Θ) as seen below:

    ______________________________________                                        Peak No.     Diffraction Angle                                                ______________________________________                                        1            9.6                                                              2            10.2                                                             3            10.4                                                             4            10.8                                                             5            12.8                                                             6            13.8                                                             7            14.2                                                             8            14.8                                                             9            15.0                                                             10           16.4                                                             11           16.8                                                             12           17.8                                                             13           18.0                                                             14           18.6                                                             15           19.0                                                             16           19.4                                                             17           19.8                                                             18           20.2                                                             19           20.6                                                             20           21.2                                                             21           21.4                                                             22           23.0                                                             23           23.4                                                             24           24.6                                                             25           26.0                                                             26           28.0                                                             27           29.0                                                             28           30.4                                                             29           31.0                                                             ______________________________________                                    

It is noted that the requirements for automotive paints and coatingshave undergone a dramatic change in recent years. This coupled withincreasing environmental concerns about the use of some aromatichydrocarbon solvents has put great pressure on the industry to come upwith new solutions to some very difficult challenges.

The benzotriazole UV absorbers have long been a mainstay in this areawith 2-[2-hydroxy-3,5-di(α-cumyl)phenyl]-2H-benzotriazole being theworkhorse and epitomy of what the benzotriazole UV absorbers candeliver. Unfortunately, this compound has only limited solubility (about14% by weight) in toluene or xylene, and is sparingly soluble inenvironmentally more friendly solvents. This is becoming a severelimitation since the aromatic solvents are on their way out because ofenvironmental concerns. Additionally, the relatively low solubility ofsaid compound even in aromatic solvents limits the total concentrationof benzotriazole UV absorber that can be added to the coating system.Since the life-time requirements for an automotive finish are doubling,the low solubility of said benzotriazole is a real hurdle.

Fortunately, there are soluble and thermally stable benzotfiazole UVabsorbers, chiefly the new soluble crystalline modification of2-(2-hydroxy-3-α-cumyl-5-tert-octyl-phenyl)-2H-benzotriazole, which hasthe same low volatility and superior light stabilization effectivenessof 2-[2-hydroxy-3,5-di(α-cumyl)phenyl]-2H-benzotriazole, but which aresoluble in environmentally friendly solvents and which can be added tothe automotive finishes at a concentration sufficiently high to meet thenew extended lifetime requirements for such finishes. This isdemonstrated in the working Examples.

The instant compositions also pertain to a composition whichadditionally contains an effective stabilizing amount of atris-aryl-s-triazine, a hindered amine light stabilizer or a mixturethereof.

Preferably such compositions contain additionally an effectivestabilizing amount of

2,4-bis-(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

2,4-bis-(2,4-dimethylphenyl)-6-(2-hydroxy-4-[3-(pentadecyloxy)-2-hydroxypropoxy]-s-triazine;

bis-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;

bis-(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;

N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide; or

N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide.

The organic material (a) stabilized in such compositions is a polymericfilm which is an acrylic/melamine resin, a polyester/melamine resin, anacrylic/urethane resin, a polyester/urethane resin, an epoxy/acid resinor a siloxane modified acrylic resin.

The instant invention also pertains to a polymer film composition whichcomprises (a) an electro coat primer in adhesion to a metal substrate;(b) a base or color coat that is in adhesion to the electrocoat andwhich comprises a film-forming binder and an organic pigment or aninorganic pigment or mixture thereof; (c) a clear coat that is inadhesion to the base coat and which comprises a film-forming binder; and(d) an effective stabilizing amount, between 1 and 20% by Weight of thefilm-forming binder, of at least one soluble and thermally stablebenzotriazole UV absorber contained in either the base coat or the clearcoat or in both base coat and clear coat, preferably in the base coat.

The polymer film composition described above can also contain anadditional layer between the electro coat primer and the base or colorcoat, which additional layer comprises (i) a film-forming binder and anorganic pigment or an inorganic pigment or mixture thereof; and (ii) aneffective stabilizing amount of at least one soluble and thermallystable benzotriazole UV absorber of formula I. Moreover, this additionallayer can also contain an effective stabilizing amount of a hinderedamine light stabilizer.

More particularly, the instant soluble and thermally stablebenzotriazoles are of formula I ##STR3## wherein R₁ is hydrogen orchloro,

R₂ is alkyl of 4 to 28 carbon atoms or --C_(m) H_(2m) COOR₄ where m is 1to 4 and R₄ is hydrogen or alkyl of 1 to 18 carbon atoms, and

R₃ is α-cumyl.

Preferably, R₁ is hydrogen,

R₂ is alkyl of 8 to 12 carbon atoms or --C_(m) H_(2m) COOR₄ where m isor 4, and R₄ is alkyl of 8 to 12 carbon atoms, and

R₃ is α-cumyl.

Most preferably, R₁ is hydrogen, R₂ is tert-octyl, nonyl or dodecyl, andR₃ is α-cumyl; and most especially where R₁ is hydrogen, R₂ is ten-octyland R₃ is α-cumyl.

A preferred embodiment of the instant invention is to a compositionstabilized against the deleterious effects of actinic light whichcomprises

(a) an organic material subject to the deleterious effects of actiniclight, and

(b) an effective stabilizing amount of a soluble benzotriazole UVabsorber which is 2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazoleor 2-(2-hydroxy-3-α-cumyl-5-dodecylphenyl)-2H-benzotriazole.

The alkyd resin lacquers which can be stabilized against the action oflight and moisture in accordance with the instant invention are theconventional stoving lacquers which are used in particular for coatingautomobiles (automobile finishing lacquers), for example lacquers basedon alkyd/melamine resins and alkyd/acrylic/melamine resins (see H.Wagner and H. F. Sarx, "Lackkunstharze" (1977), pages 99-123). Othercrosslinking agents include glycouril resins, blocked isocyanates orepoxy resins.

The lacquers stabilized in accordance with the invention are suitableboth for metal finish coatings and solid shade finishes, especially inthe case of retouching finishes, as well as various coil coatingapplications. The lacquers stabilized in accordance with the inventionare preferably applied in the conventional manner by two methods, eitherby the single-coat method or by the two-coat method. In the lattermethod, the pigment-containing base coat is applied first and then acovering coat of clear lacquer over it.

It is also to be noted that the compounds of the present invention areapplicable for use in non-acid catalyzed thermoset resins such as epoxy,epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionallymodified with silicon, isocyanates or isocyanurates. The epoxy andepoxy-polyester resins are crosslinked with conventional crosslinkerssuch as acids, acid anhydrides, amines and the like. Correspondingly,the epoxide may be utilized as the crosslinking agent for variousacrylic or polyester resin systems that have been modified by thepresence of reactive groups on the backbone structure.

When used in two-coat finishes, the compounds of the instant inventioncan be incorporated in the clear coat or both in the clear coat and inthe pigmented base coat.

To attain maximum light stabilization, the concurrent use of otherconventional light stabilizers can be advantageous. Examples of suchstabilizers are UV absorbers of the benzophenone, benzotriazole,cyanoacrylate or oxanilide type, or metal-containing light stabilizers,for example, organic nickel compounds, or hindered amine lightstabilizers. In two-coat systems, these additional light stabilizers canbe added to the clear coat or both in the clear coat and in the pigmentsbase coat.

The instant compositions also pertain to a composition whichadditionally contains an effective stabilizing amount of atris-aryl-s-triazine, a hindered amine light stabilizer or a mixturethereof.

Preferably such compositions contain additionally an effectivestabilizing amount of

2,4-bis-(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

2,4-bis-(2,4-dimethylphenyl)-6-(2-hydroxy-4-[3-(pentadecyloxy)-2-hydroxypropoxy]-s-triazine;

bis-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;

bis-(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;

N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide; or

N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide.

The organic material (a) stabilized in such compositions is a polymericfilm which is an acrylic/melamine resin, a polyester/melamine resin, anacrylic/urethane resin, a polyester/urethane resin, an epoxy/acid resinor a siloxane modified acrylic resin.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polyethylene(which optionally can be crosslinked), polypropylene, polyisobutylene,polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, aswell as polymers of cycloolefins, for instance of cyclopentene ornorbornene.

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, such as, for example, ethylene/propylene,propylene/butene-1, propylene/isobutylene, ethylene/butene-1,propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates,ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylicacid copolymers and their salts (ionomers) and terpolymers of ethylenewith propylene and a diene, such as hexadiene, dicyclopentadiene orethylidene-norbornene.

4. Polystyrene, poly-(et-methylstyrene).

5. Copolymers of styrene or methylstyrene with dienes or acrylicderivatives, such as, for example, styrene/butadiene,styrene/acrylonitrile, styrene/ethyl methacrylate,styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength from styrene copolymers and anotherpolymer, such as, for example, from a polyacrylate, a diene polymer oran ethylene/propylene/diene terpolymer; and block polymers of styrene,such as, for example, styrene/butadiene/styrene,/isoprene/styrene,ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, such as, for example, styrene onpolybutadiene, styrene and acrylonitrile on polybutadiene, styrene andalkyl acrylates or methacrylates on polybutadiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyacrylates or polymethacrylates, styrene andacrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 5), for instance the copolymermixtures known as ABS-, MBS-, ASA- or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrinhomo- and copolymers, polymers from halogen-containing vinyl compounds,as for example, polyvinylchloride, polyvinylidene chloride, polyvinylfluoride, polyvinylidene fluoride, as well as copolymers thereof, as forexample, vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate, vinylidene chloride/vinyl acetate copolymers, or vinylfluoride/vinyl ether copolymers.

8. Polymers which are derived from α,β-unsaturated acids and derivativesthereof, such as polyacrylates and polymethacrylates, polyacrylamide andpolyacrylonitrile.

9. Copolymers from the monomers mentioned under 8) with each other orwith other unsaturated monomers, such as, for instance,acrylonitrilefoutadiene, acrylonitrile/alkyl acrylate,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenidecopolymers or acrylonitrile/alkyl methacrylatefoutadiene terpolymers.

10. Polymers which are derived from unsaturated alcohols and amines, oracyl derivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as comonomer.

13. Polyphenylene oxides and surfides, and mixtures of polyphenyleneoxides with polystyrene.

14. Polyurethanes which are derived from polyethers, polyesters orpolybutadienes with terminal hydroxyl groups on the one side andaliphatic or aromatic polyisocyanates on the other side, as well asprecursors thereof (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,polyamide 6/10, polyamide 11, polyamide 12,poly-2,4,4-trimethylhexamethylene terephthalamide, poly-p-phenyleneterephthalamide or poly-m-phenylene isophthalamide, as well ascopolymers thereof with polyethers, such as for instance withpolyethylene glycol, polypropylene glycol or polytetramethylene glycols.

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and diolsand/or from hydroxycarboxylic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylol-cyclohexane terephthalate,poly-[2,2-(4-hydroxyphenyl)-propane] terephthalate andpolyhydroxybenzoates as well as block-copolyether-esters derived frompolyethers having hydroxyl end groups.

18. Polycarbonates.

19. Polysulfones, polyethersulfones and polyetherketones.

20. Crosslinked polymers which are derived from aldehydes on the onehand and phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

23. Thermosetting acrylic resins, derived from substituted acrylicesters, such as epoxy-acrylates, urethane-acrylates or polyesteracrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture withmelamine resins, urea resins, polyisocyanates or epoxide resins ascrosslinking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, forexample from bis-glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatin and derivativesthereof which are chemically modified in a polymer homologous manner,such as cellulose acetates, cellulose propionates and cellulosebutyrates, or the cellulose ethers, such as methyl cellulose.

27. Mixtures of polymers as mentioned above, for example PP/EPDM,Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS.

28. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, which materials may be used as plasticizers forpolymers or as textile spinning oils, as well as aqueous emulsions ofsuch materials.

29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

30. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

31. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

32. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

33. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE-4103 (Monsanto).

In general, the compounds of the present invention are employed fromabout 1 to about 20% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from 1 to 5%; preferably 1.5 to 2.5%.

The resulting stabilized compositions of the instant invention mayoptionally also contain from about 0.01 to about 5%, preferably fromabout 0.025 to about 2%, and especially from about 0.1 to about 1% byweight of various conventional additives, such as the materials listedbelow, or mixtures thereof.

Other compositions of special interest include those which additionallycontain a UV absorber selected from the group consisting of thebenzophenones, benzotriazoles, cyanoacrylic acid derivatives,hydroxyaryl-s-triazines, organic nickel compounds and oxanilides.

Preferred UV absorbers are selected from the group consisting of2-[2-hydroxy-3,5-di-(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-[2-hydroxy-3-tert-butyl-5-(ω-hydroxy-octa(ethyleneoxy)carbonyl)ethylphenyl]-2H-benzotriazole,2-[2-hydroxy-3-tert-butyl-5-(2-octyloxycarbonylethyl)phenyl]-2H-benzotriazole,4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide,2,2'-didodecyl-oxy-5,5'-di-tert-butyloxanilide,2-ethoxy-2'ethyloxanilide,2,6-bis(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl-s-triazine,2,6-bis(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-,2,6-bis(2,4-dimethylphenyl)-4-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropanoxy)phenyl]-s-triazineand 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

Additional compositions of interest include those which additionallycontain an effective stabilizing amount of a phenolic antioxidant; thosewhich additionally contain a hindered amine derivative; or whichadditionally contain a phosphite or phosphonite stabilizer.

Compositions of special interest also include those wherein the organicmaterial is an enamel of high solids content used for an industrialfinish; is used as a coil coating; is used as a penetrating wood finishor is used as a film-forming wood finish.

When the instant compounds also contain a reactive functional group,said compounds can be chemically bonded by either condensation or freeradical addition reaction to the polymer substrate. This provides for anon-migrating, non-sublimable UV absorber stabilizer. Such reactivefunctional groups include hydroxy, amino, amido, carboxyl andethylenically unsaturated moieties.

The various organic materials useful in the instant invention aredescribed in detail later in this application as well as are the variouscoadditives whose concomitant use with the instant compounds is oftenfound to be highly beneficial.

The resulting stabilized polymer compositions of the invention mayoptionally also contain from about 0.01 to about 5%, preferably fromabout 0,025 to about 2%, and especially from about 0.1 to about 1% byweight of various conventional additives, such as the materials listedbelow, or mixtures thereof.

1. Antioxidants

1.1. Alkylated monophenols, for example,

2,6-di-tert-butyl-4-methylphenol

2-tert-butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,5-di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example,

2,2'-thio-bis-(6-tert-butyl-4-methylphenol)

2,2'-thio-bis-(4-octylphenol)

4,4'-thio-bis-(6-tert-butyl-3-methylphenol)

4,4'-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2'-methylene-bis-(6-nonyl-4-methylphenol)

2,2'-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

4,4'-methylene-bis-(2,6-di-tert-butylphenol)

4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol       diethylene glycol                                              octadecanol    triethylene glycol                                             1,6-hexanediol pentaerythritol                                                neopentyl glycol                                                                             tris-hydroxyethyl isocyanurate                                 thiodiethylene glycol                                                                        di-hydroxyethyl oxalic acid diamide                            ______________________________________                                    

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol       diethylene glycol                                              octadecanol    triethylene glycol                                             1,6-hexanediol pentaerythritol                                                neopentyl glycol                                                                             tris-hydroxyethyl isocyanurate                                 thiodiethylene glycol                                                                        di-hydroxyethyl oxalic acid diamide                            ______________________________________                                    

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

2. UV absorbers and light stabilizers

2.1 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,3',5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-,3'-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3',5'-di-tert-amyl-,3',5'-bis-(α,α-dimethylbenzyl),3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-,and dodecylated-5'-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyano vinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetra-methylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl)sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl)sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octyl-amino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacelate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).

2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-4-(2-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-;2,4-bis-(2,4-dimethylphenyl)-6-{2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl}-s-triazine;2,4-bis-(2,4-dimethylphenyl)-6-{2-hydroxy-4-[3-(pentadecyloxy)-2-hydroxypropoxy]phenyl}-s-triazine.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4'-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-hepta-decyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydmgenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazincderivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fauy acids for example Ca stearate,Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimonypyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tertbutyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2'-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tertbutyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N'-bis-[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2'-ethylidene-bis(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N'"-tetrakis[(4,6-bis-(butyl-2,2,6,6-tetramethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl,β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethyl]1,2,3,4-butanetetracarboxylate,octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethypiperidin-4-yl)-n-butylamino]-6-[di-(2-hydroxyethyl)amino]-s-triazine,and2,4-bis[N-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-6-[di-(2-hydroxyethyl)amino]-s-triazine.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octyl-amino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N'"-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

The process for the preparation of the soluble crystalline modificationof the compound of formula I which is2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole comprisescrystallizing or recrystallizing said compound of formula I from analkanol of 1 to 4 carbon atoms either alone or in conjunction with aminor amount (up to 10% by volume) of toluene. Preferably the alkanol isan alkanol of 3 to 4 carbon atoms; most preferably isopropanol or1-butanol.

Some alkanols useful in the instant process are, for example, methanol,ethanol, n-propanol, isopropanol, 1-butanol, sec-butyl alcohol orisobutyl alcohol.

Still another aspect of the instant invention is the application of theinstant compounds of formula I in recording materials. The recordingmaterials according to the invention are suitable for pressure-sensitivecopying systems, photocopying systems using microcapsules,heat-sensitive copying systems, photographic materials and ink jetprinting.

The recording materials according to the invention are distinguished byan unexpected improvement in quality, especially with regard to thefastness to light.

The recording materials according to the invention have the constructionknown for the particular use. They consist of a customary carrier, forexample paper or plastic film, which has been coated with one or morelayers. Depending on the type of the material, these layers contain theappropriate necessary components, in the case of photographic materials,for example, silver halide emulsions, dye couplers, dyes and the like.Material particularly suitable for ink jet printing has a layerparticularly absorptive for ink on a customary carrier. Uncoated papercan also be employed for ink jet printing. In this case the paper actsat the same time as the carrier material and as the ink-absorbent layer.Suitable material for ink jet printing is, for example, described inU.S. Pat. No. 5,073,448 (incorporated herein by reference).

The recording material can also be transparent, as, for example, in thecase of projection films.

The compounds of the formula I can be incorporated into the carriermaterial as early as the production of the latter, in the production ofpaper, for example, by being added to the paper pulp. A second method ofapplication is to spray the carrier material with an aqueous solution ofcompounds of the formula I or to add the compounds of the formula I tothe coating composition.

Coating compositions intended for transparent recording materialssuitable for projection cannot contain any particles which scatterlight, such as pigments and fillers.

The dye-binding coating composition can contain a number of otheradditives, for example antioxidants, light stabilizers (including alsoUV absorbers which do not belong to the UV absorbers according to theinvention), viscosity improvers, fluorescent brighteners, biocidesand/or antistatic agents.

The coating composition is usually prepared as follows: thewater-soluble components, for example the binder, are dissolved in waterand stirred together. The solid components, for example fillers andother additives already described, are dispersed in this aqueous medium.Dispersion is advantageously carded out by means of devices, for exampleultrasonic samples, turbine stirrers, homogenizers, colloid mills, beadmills, sand mills, high-speed stirrers and the like. It is a particularadvantage of the compounds of the formula I that they can beincorporated easily into the coating composition.

The recording material according to this invention preferably contains 1to 5000 mg/m², in particular 50-1200 mg/m², of a compound of the formulaI.

As already mentioned, the recording materials according to the inventionembrace a wide field. The compounds of the formula I can, for example,be employed in pressure-sensitive copying systems. They can beintroduced either into the paper in order to protect themicroencapsulated dye precursors there from light, or into the binder ofthe developer layer in order to protect the dyes formed there.

Photocopying systems using light-sensitive microcapsules which aredeveloped by means of pressure are described in U.S. Pat. Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,5365,463; 4,551,407;4,562,137 and 4,608,330, also in EP-A 139,479; EP-A 162,664; EP-A164,931; EP-A 237,024; EP-A 237,025 or EP-A 260,129. In all thesesystems the compounds of the formula I can be put into the dye-receivinglayer. The compounds of the formula I can, however, also be put into thedonor layer in order to protect the colour formers from light.

Photographic materials which can be stabilized are photographic dyes andlayers containing such dyes or precursors thereof, for examplephotographic paper and films. Suitable materials are, for example,described in U.S. Pat. No. 5,364,749 (incorporated therein byreference). The compounds of the formula I act here as a UV filteragainst electrostatic flashes. In colour photographic materials couplersand dyes are also protected against photochemical decomposition.

The compounds of the formula I can be used for all types of colourphotographic materials. For example, they can be employed for colourpaper, colour reversal paper, direct-positive colour material, colournegative film, colour positive film, colour reversal film, etc. They arepreferably used, inter alia, for photographic colour material whichcontains a reversal substrate or forms positives.

Colour-photographic recording materials usually contain, on a support, ablue-sensitive and/or a green-sensitive and/or a red-sensitivesilver-halide emulsion layer and, if desired, a protection layer, thecompounds of formula I being, preferably, either in the green-sensitiveor the red-sensitive layer or in a layer between the green-sensitive andthe red-sensitive layer or in a layer on top of the silver-halideemulsion layers.

The compounds of the formula I can also be employed in recordingmaterials based on the principles of photopolymerization,photoplasticization or the rupture of microcapsules, or in cases whereheat-sensitive and light-sensitive diazonium salts, leuko dyes having anoxidizing agent or dye lactones having Lewis acids are used.

Furthermore, they can be employed in recording materials for dyediffusion transfer printing, thermal wax transfer printing and dotmatrix printing and for use with electrostatic, electrographic,electrophoretic, magnetographic and laser-electrophotographic printersand pen-plotters. Of the above, recording materials for dye diffusiontransfer printing are preferred as, for example described inEP-A-507,734.

The compounds of the formula I can also be employed in inks, preferablyfor ink jet printing, as, for example, further described in U.S. Pat.No. 5,098,477 (incorporated herein by reference). A further subject ofthe present invention is, therefore, an ink containing at least onecompound of the formula I as a stabilizer. The ink, particularly for inkjet printing, preferably contains water. Inks containing the stabilizerof the formula I in a concentration of 0.01 to 20% by weight,particularly 0.5 to 10% by weight, are also preferred.

X-ray diffraction patterns are recorded on a Philips Norelco X-rayDiffractometer unit, using Cu-Kα radiation with a nickel filter. Allsamples have a uniform particle size of 40 to 75 microns. This is thesame particle size distribution obtained with the prior art compound ofExample 2.

The following examples are presented for the purpose of illustrationonly and are not to be construed to limit the nature or scope of theinstant invention in any manner whatsoever.

EXAMPLE 1 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The compound of formula I,2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, is preparedaccording to the general procedure of Example 18 of U.S. Pat. No.4,278,589. A 300 g sample of the compound of formula I is dissolved in300 mL of xylene. To this solution is then added with stirring 600 mL ofethanol to afford 254 g of the novel soluble crystalline modification ofthe compound of formula I having a melting point of 109°-111 ° C.; andexhibiting only one spot in thin layer chromatography.

Analysis: Calcd for C₂₉ H₃₅ N₃ O: C, 78.9; H, 8.0; N, 9.5. Found: C,78.7; H; 8.1; N, 9.6.

This product has an X-ray diffraction pattern obtained using Cu-Kα whichexhibits diffraction angles (2θ) as seen below:

    ______________________________________                                        Peak No.     Diffraction Angle                                                ______________________________________                                        1            9.6                                                              2            10.2                                                             3            10.4                                                             4            10.8                                                             5            12.8                                                             6            13.8                                                             7            14.2                                                             8            14.8                                                             9            15.0                                                             10           16.4                                                             11           16.8                                                             12           17.8                                                             13           18.0                                                             14           18.6                                                             15           19.0                                                             16           19.4                                                             17           19.8                                                             18           20.2                                                             19           20.6                                                             20           21.2                                                             21           21.4                                                             22           23.0                                                             23           23.4                                                             24           24.6                                                             25           26.0                                                             26           28.0                                                             27           29.0                                                             28           30.4                                                             29           31.0                                                             ______________________________________                                    

EXAMPLE 2 Comparative Example2-(2-Hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The title compound is prepared as described in Example 18 of U.S. Pat.No. 4,278,589 as off-white crystals melting at 88°-90° C. This compoundof formula I exhibits an X-ray diffraction pattem obtain using Cu-Kαwhich exhibits diffraction angles (2θ) as seen below:

    ______________________________________                                        Peak No.     Diffraction Angle                                                ______________________________________                                        1            5.2                                                              2            6.2                                                              3            6.8                                                              4            9.2                                                              5            9.7                                                              6            11.0                                                             7            12.0                                                             8            12.2                                                             9            13.0                                                             10           13.6                                                             11           14.6                                                             12           15.4                                                             13           15.6                                                             14           16.4                                                             15           17.8                                                             16           18.8                                                             17           19.4                                                             18           19.8                                                             19           20.4                                                             20           21.0                                                             21           22.4                                                             22           22.8                                                             23           23.4                                                             24           24.2                                                             25           25.0                                                             26           25.4                                                             27           26.0                                                             28           27.6                                                             29           29.4                                                             30           30.8                                                             31           31.2                                                             32           32.4                                                             ______________________________________                                    

A comparison of the X-ray diffraction patterns of the instant solublecrystalline modification as seen in Example 1 with the X-ray diffractionpattern of the prior art compound of Example 18 of U.S. Pat. No.4,278,589 clearly indicates that the two materials are not the same.

EXAMPLE 3 Amorphous form of2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The compound prepared in Example 1 is heated to a melt and then allowedto resolidify. The amorphous material obtained has a melting point of59°-74° C. Thin layer chromatography exhibits one spot identical to thatobtained from the product of Example 1.

X-ray diffraction shows a featureless pattern confuming the amorphousnature of the compound obtained in this example.

EXAMPLE 4 2-(2-Hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole

The title compound is prepared according to the general procedure ofExample 18 of U.S. Pat. No. 4,278,589 as an amber resin, but where thereduction of the corresponding o-nitroazobenzene intermediate is carriedout using catalytic hydrogenation.

Analysis: Calcd for C₃₀ H₃₇ N₃ O: C, 79.1; H, 8.2; N, 9.2. Found: C,79.5; H, 8.5; N, 9.0.

EXAMPLE 55-Chloro-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole

The title compound is prepared according to the general procedure ofExample 18 of U.S. Pat. No. 4,278,589 as a pale yellow oil.

EXAMPLE 6 2-(2-Hydroxy-3-tert-octyl-5-α-cumylphenyl)-2H-benzotriazole

The title compound is prepared as described in Example 19 of U.S. Pat.No. 4,278,589.

EXAMPLE 7 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

The title compound is prepared by the catalytic hydrogenation of theo-nitroazobenzene intermediate described in Example 17 of U.S. Pat. No.4,278,589 as an off-white solid. A 100 g sample of said solid isrecrystallized from 100 mL of isopropanol, again from 100 mL of 19:1isopropanol:toluene and finally from 100 mL of 9:1 isopropanol:tolueneto afford 78 g of the title compound melting at 109-111° C and havingthe same crystalline modification and X-ray diffraction pattern as thecompound prepared in Example 1.

EXAMPLE 8 2-(2-Hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole

The title compound is prepared according to the general procedure ofExample 18 of U.S. Pat. No. 4,278,589 as an amber resin.

EXAMPLE 9 2-(2-Hydroxy-3-α-cumyl-5-dodecylphenyl)-2H-benzotriazole

The title compound is prepared according to the general procedure ofExample 18 of U.S. Pat. No. 4,278,589 as an amber resin.

EXAMPLE 10 2-(2-Hydroxy-3-α-cumyl-5-dodecylphenyl)-2H-benzotriazole

The title compound is prepared according to the general procedure ofExample 18 of U.S. Pat. No. 4,278,589 as an amber resin, but where thereduction of the corresponding o-nitroazobenzene intermediate is cardedout using catalytic hydrogenation.

EXAMPLES 11-12

Following the general procedure of Examples 1 and 7, the followingcompounds of formula I are prepared where R₂ is hydrogen and R₃ isα-cumyl.

    ______________________________________                                        Example                                                                              R.sub.2                                                                ______________________________________                                        11     --CH.sub.2 CH.sub.2 COOCH.sub.3                                        12     --CH.sub.2 CH.sub.2 COOC.sub.8 H.sub.17                                ______________________________________                                    

EXAMPLE 13 Solubility in Organic Solvents

In order to incorporate a UV absorber stabilizer into the high solidsthermoset acrylic resin systems, the UV absorber must be soluble in anappropriate organic solvent. To date solvents such as the aromatichydrocarbons, toluene or xylene, have provided ample solubility for suchUV absorbers, even the sparingly soluble2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole.

However, the possible phasing out of such aromatic hydrocarbon solventsfor environmental reasons, the trend to higher solids coatings, and theincreasing demands of the automobile industry for automotive coatingsthat will last for up to 10 years means that a more soluble,non-volatile, but equally effective UV absorber will be required.Additionally, the UV absorber must be soluble in an environmentallyfriendly solvent.

The relative solubility of three different benzotriazole UV absorbers ina five typical organic solvents is measured by dissolving thebenzotriazole UV absorber in 50-100 mL of five different solvents tillthe solutions become supersaturated. This is seen when the benzotriazolebegins to settle to the bottom of the test flask. The supersaturatedsolutions are allowed to remain undisturbed overnight. Then, the toplayer is decanted and filtered. The resulting flitrate containing thebenzotriazole dissolved in the solvent is tested in triplicate forpercent solids using ASTM Test Method D 2369-81. The higher the percentsolids found indicates a more soluble benzotriazole. The results areseen in the table below.

    ______________________________________                                        Benzotriazole*                                                                Solubility in grams/100 solvent                                                           UV Absorber                                                       Solvent**     A       B     C     D    E                                      ______________________________________                                        xylene        14      54    76    >50  >50                                    butyl acetate 6       27    33    >50  >50                                    methyl amyl ketone                                                                          4       24    33    >50  >50                                    acetone       --      --    --    >50  >50                                    EXXATE ® 600                                                                            4       24    22    >50  >50                                    PM acetate    3       10    4     >50  >50                                    PM solvent    --       4    4     --   --                                     ______________________________________                                         *A is 2(2-hydroxy-3,5-di-cumylphenyl)-2H-benzotriazole.                       B is 2(2-hydroxy-3,5-di-tert-amylphenyl-2H-benzotriazole.                     C is the compound of Example 7.                                               D is the compound of Example 4.                                               E is the compound of Example 10.                                              **EXXATE ® 600 is hexyl acetate from Exxon.                               PM acetate is 1methoxy-2-propyl acetate.                                      PM solvent is 1methoxy-2-propanol.                                       

Xylene is now a regulated solvent and is listed as a HAP's solvent(Hazardous Air Pollutant). As such, xylene is rapidly becoming phasedout as a solvent for all types of coatings and an appropriate solventsubstitute is becoming mandatory.

The other solvents listed in the table above are not currently targetedfor regulation or removal and are becoming more common in the coatingsindustry.

The recent trend in the coatings industry is to higher solids coatingswhich means even less solvent to dissolve the UV absorber. The need fora more soluble, non-volatile UV absorber is most evident.

Inspection of the data in the table shows that UV absorber A is clearlyless soluble in each of the solvents than is UV absorber B or C. Infact, the solubility of UV absorber A in any solvent other than xyleneessentially removes it from consideration as a practical stabilizer inthe new long term automotive coatings under the constraints listedabove.

UV absorber B is clearly quite soluble even in the solvents other thenxylene, but UV absorber B is too volatile for long term coating uses.

This leaves UV absorbers C-E which are even more soluble than UVabsorber B, but also have the excellent non-volatility exhibited by UVabsorber A. This combination of properties makes UV absorbers C-E primecandidates for use in long-term automotive high solids coatings.

EXAMPLE 14

The amorphous modification of2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole as preparedin Example 3 exhibits essentially the same solubility parameters in thevarious solvents as seen in Example 13 for the new crystallinemodification of2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole prepared inExample 1 or 7 except that the amorphous form of2-(2-hydroxy-3-α-cumyl-5-tert-octyl-phenyl)-2H-benzotriazole dissolvesmuch more easily and rapidly in the non-HAPS solvents. This is adistinct advantage for using the amorphous compound of Example 3 inpractical applications.

EXAMPLE 15 Gloss Retention of High Solids Thermoset Acrylic Clear CoatsContaining UV Absorbers Applied Directly over a Silver Metallic BaseCoat and a Electro Coat Primer

Coated panels are prepared by spray applying a 1.8-2.0 mil (0.072-0.102mm) thick film of a model HAPS-compliant high solids thermoset acrylicmelamine clear coat containing 2% by weight of a test stabilizer over acommercially available silver metallic base coat, wet-on-wet, directlyonto 4"×12" (10.16 cm×30.48 cm) UNIPRIME® panels obtained from AdvancedCoating Technology, Inc. containing an electro coat primer. The coatedpanels axe then baked at 250° F (121° C) for thirty minutes. The coatedpanels are then exposed in a Ci-65 Weather-O-meter (Atlas ElectricDevices) according to ASTM G 26-90. The gloss of the exposed panels ismeasured at 300 hour intervals. Higher gloss indicates greaterprotecting afforded to the coating by the soluble benzotriazole UVabsorber.

The instant soluble compounds of formula I provide the coatings withgood gloss retention.

Indeed, because a much higher concentration of soluble benzotriazole canbe conveniently incorporated into the coating, the solublebenzotriazoles provide gloss retention for the high solids thermosetacrylic coating system far beyond that obtained where only a limitedamount of benzotriazole is possible because of solubility limitations.

EXAMPLE 16 Gloss Retention of High Solids Thermoset Acrylic Clear CoatsContaining UV Absorbers Applied Directly over a Silver Metallic BaseCoat and a Electro Coat Primer

Coated panels prepared as in Example 15 are also exposed in a QUVexposure device (Q Panel Co.) according to ASTM G 53. The 20° gloss isagain measure at 300 hour intervals with higher gloss values indicatinggreater protection of the coating.

The instant soluble compounds of formula I provide the coatings withgood gloss retention.

Indeed, because a much higher concentration of soluble benzotriazole canbe conveniently incorporated into the coating, the solublebenzotriazoles provide gloss retention for the high solids thermosetacrylic coating system far beyond that obtained where only a limited aamount of benzotriazole is possible because of solubility limitations.

Indeed, panels stabilized with a soluble benzotriazole UV absorber offormula I exhibit at least 50% gloss retention after 3000 hours in theQUV exposure device.

EXAMPLE 17 Gloss Retention of Acrylic Urethane Clear Coats Containing UVAbsorbers Applied Directly over a Silver Metallic Base Coat and aElectro Coat Primer

Coated panels are prepared by spray applying a 1.8-2.0 mil (0.036-0.051mm) thick film of a model HAPS-compliant high solids acrylic urethaneclear coat containing a test stabilizer over a commercially availablesilver metallic base coat, wet-on-wet, directly over 4"×12" (10.16cm×30.48 cm) UNIPRIME® panels obtained from Advanced Coating Technology,Inc. containing an electro coat primer. The coated panels are then bakedat 250° F. (121° C.) for thirty minutes. The coated panels are thenexposed in a Ci-65 Weather-O-meter (Atlas Electric Devices) according toASTM G 26-90. The gloss of the exposed panels is measured at 300 hourintervals. Higher gloss indicates greater protection afforded to thecoating by the soluble benzotriazole UV absorber.

The instant soluble compounds of formula I provide the coatings withgood gloss retention.

Indeed, because a much higher concentration of soluble benzotriazole canbe conveniently incorporated into the coating, the solublebenzotriazoles provide gloss retention for the high solids thermosetacrylic coating system far beyond that obtained where only a limitedamount of benzotriazole is possible because of solubility limitations.

EXAMPLE 18 Gloss Retention of Acrylic Urethane Clear Coats Containing UVAbsorbers Applied Directly over a Silver Metallic Base Coat and aElectro Coat Primer

Coated panels prepared as in Example 17 are also exposed in a QUVexposure device (Q Panel Co.) according to ASTM G 53. The 20° glass isagain measure at 300 hour intervals with higher gloss values indicatinggreater protection of the coating.

The instant soluble compounds of formula I provide the coatings withgood gloss retention.

Indeed, because a much higher concentration of soluble benzotriazole canbe conveniently incorporated into the coating, the solublebenzotriazoles provide gloss retention for the high solids thermosetacrylic coating system far beyond that obtained where only a limitedamount of benzotriazole is possible because of solubility limitations.

EXAMPLE 19 UVA Retention in High Solids Thermoset Acrylic Clear CoatsApplied Directly over a Quartz Microscope Slide

Coated quartz microscope slides are prepared by spray application of a0.9-1.0 mil (0.018-0,026 mm) thick film of a model HAPS-compliant highsolids thermoset acrylic melamine clear coat containing a test UVabsorber. The coated quartz slides are then baked at 250° F. (121° C.)for 30 minutes. The optical density of the films is then measured at 345nm.

The coated quartz slides are then exposed in a QUV exposure device (QPanel Co.) according to ASTM G 53. The optical density is then measuredagain at 1000 hour intervals with higher optical density valuesindicating greater protection of the coating.

The instant soluble compounds of formula I provide the coatings withhigher optical density values at all intervals.

Indeed, because a much higher concentration of soluble benzotriazole canbe conveniently incorporated into the coating, the solublebenzotriazoles provide UVA retention for the high solids thermosetacrylic coating system far beyond that obtained where only a limitedamount of benzotriazole is possible because of solubility limitations.

EXAMPLE 20 UVA Retention in High Solids Thermoset Acrylic Clear CoatsApplied Directly over a Quartz Microscope Slide

Coated quartz microscope slides are prepared according to the directionsof Example 19. These coated slides are also exposed in a Ci-65Weather-Ometer (Atlas Electric Devices) according to ASTM G-26-90. Theoptical density is measured at 1000 hour intervals with higher opticaldensity values indicating greater protection of the coating.

The instant soluble compounds of formula I provide the coatings withhigher optical density values at all intervals.

Indeed, because a much higher concentration of soluble benzotriazole canbe conveniently incorporated into the coating, the solublebenzotriazoles provide UVA retention for the high solids thermosetacrylic coating system far beyond that obtained where only a limitedamount of benzotriazole is possible because of solubility limitations.

EXAMPLE 21

The amount of UV absorber shown in the table below is dissolved in 2 mlof ethyl acetate. 1 ml of this solution is mixed with 9 ml of an aqueousgelatine solution [comprising 27.6 g/l of gelatine and 6.8 g/l of an 8%aqueous solution of 4,8-diisobutylnaphthalene-2-sulfonic acid (sodiumsalt) as wetting agent]. This mixture is emulsified for 3 minutes bymeans of ultrasound. 7.5 ml of this UV absorber emulsion are mixed with4.5 ml of an aqueous curing agent solution (comprising 0.24% of2-hydroxy-4,6-dichloro-s-triazine, potassium salt). 8 ml of thisemulsion are poured onto a polyester base (13×18 cm). The casting iscured for 7 days at room temperature. A UV spectrometer is then used todetermine the values for the maximum density in the range from 330-380nm. The sample is then exposed in an Atlas exposure unit with a total of30, 60, 90 and 120 kJ/cm², the maximum density is remeasured, and thedifference (-ΔD in %) between the corresponding values is calculated.The smaller is the ΔD value, the more stable is the UV absorber.

    ______________________________________                                                       ΔD in %                                                  Comopund* D.sub.max                                                                            mg/m.sup.2                                                                            30 KJ 60 KJ 90 KJ 120 KJ                             ______________________________________                                        A         2.0    492     4     8     16    25                                 B         2.1    640     5      10   17    25                                 C         2.1    560     4     7     12    24                                 D         1.9    560     0     5     --    --                                 E         2.0    660     3     4      5     7                                 F         1.9    726     2     4      5     8                                 ______________________________________                                         *A is 2(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole.           B is 2(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole.                  C is 2(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole.                    D is 2(2-hydroxy-3,5-di-cumylphenyl)-2H-benzotriazole.                        E is 2(2-hydroxy-3-cumyl-5-tert-octylphenyl)-2H-benzotriazole.                F is 2(2-hydroxy-3-cumyl-5-dodecylphenyl)-2H-benzotriazole.              

It is clear that the UV absorbers A, B and C which are not substitutedwith an α-cumyl group at the 3-position of the 2-phenyl ring are not asphotostable as the UV absorbers D, E and F which have such α-cumylsubstitution. UV absorber D with two α-cumyl groups is no more stablethan are UV absorbers E and F which have only one such α-cumyl group inthe 3-position, but which do not suffer from the solubility limitationsof UV absorber D in non-HAPS solvents described earlier in thisSpecification.

What is claimed is:
 1. The compound which is2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole.
 2. The compoundwhich is 2-(2-hydroxy-3-α-cumyl-5-dodecylphenyl)-2H-benzotriazole.